Heat-curable compositions comprising a mixture of bis(2-hydroxyethyl)dicyclopentadiene-containing polyesters and unsaturated polyesters

ABSTRACT

Novel heat-curable compositions are obtained by combining a bis(2-hydroxyethyl)dicyclopentadiene-containing polyester and an unsaturated polyester. These compositions can be cross-linked by heating at temperatures above 135 DEG  C., and do not require cross-linking agents or radical initiators. The compositions of the present invention are useful as coatings and adhesives having superior qualities.

FIELD OF THE INVENTION

The invention relates to heat-curable compositions useful as coatingsand adhesives. More specifically, the invention relates to heat-curablecompositions which comprise a mixture ofbis(2-hydroxyethyl)dicyclopentadiene-containing polyesters andunsaturated polyesters.

BACKGROUND OF THE INVENTION

In most enamel coatings and adhesives, cross-linking is effected in oneof two ways: either a reaction of cross-linking agents such asmelamine-formaldehyde takes place with either the carboxyl or hydroxylfunctionality of a polymer, or a free radical reaction occurs whichproduces a three-dimensional polymer network. The free radical reactionsrequire use of a radical initiator in order to proceed. Furthermore,reactions such as these often involve the liberation of volatile organicby-products which necessitates expensive and cumbersome containment ofthese procuts. It would thus be desirable to obtain polymer coatings andadhesives of superior quality, yet which do not require cross-linkingagents or radical initiators, and which do not liberate volatile organicby-products.

SUMMARY OF THE INVENTION

It has been discovered that the combination of polyesters containingbis(2-hydroxyethyl)dicyclopentadiene and unsaturated polyesters resultsin an unexpected and unique cross-linking reaction which does notrequire cross-linking agents or radical initiators, and does notliberate volatile organic by-products. As a result of the cross-linkingsystem of the reaction, novel three-dimensional cross-linkedcompositions are obtained when these polyesters are reacted attemperatures of 160°-200° C. The compositions are useful as coatingshaving excellent hardness, flexibility and solvent resistance, and asadhesives which have strong metal-metal bonding characteristics.

DETAILED DESCRIPTION OF THE INVENTION

The novel heat-curable compositions of the present invention areobtained by combining a film or fiber forming polyester containingbis(2-hydroxyethyl)-dicyclopentadiene (hereinafter BHDP) and comprisingrecurring units of the formula: ##STR1## wherein R is an aliphatic oraromatic group, with an unsaturated polyester. These compositions arecurable at temperatures above 135° C. and provide a resinous productuseful as a coating or an adhesive. When the BHDP-containing polyestersare reacted with unsaturated polyesters at elevated temperatures, anovel and unexpected cross-linking reaction occurs to give a cured,three dimensional polymer network.

Reacting the BHDP-polyesters with unsaturated polyesters at temperaturesin the range of about 160° C. to about 200° C. is usually sufficient toform the cross-linked, three dimensional product. At these reactiontemperatures the BHDP-polyester cracks to give the followingcyclopentadiene appendages: ##STR2## The dienes then react with theunsaturated polyester having the formula represented as: ##STR3##wherein R' represents a straight or branched chain aliphatic group of 2to 12 carbon atoms, an aromatic group of 6 to 12 carbon atoms, or agroup of the formula: ##STR4## wherein each R" is, independently, astraight or branched chain aliphatic group of 2 to 12 carbon atoms andR"' is a straight or branched aliphatic group of 0 to 12 carbon atoms.Preferred R' groups are methylene; bismethylene; trimethylene;tetramethylene; ortho-, meta- or para-phenylene; methylphenylene;ethylphenylene; and the like. A Diels-Alder reaction occurs forming aproduct schematically indicated as: ##STR5##

A secondary cross-linking reaction also occurs under the curingconditions. Radical intermediates are generated in the air oxidation ofthe dicyclopentadiene moiety. These radicals react with either themaleate double bond or those present in other dicyclopentadiene units,thus building a three-dimensional cross-linked network.

The above reaction can be carried out in any reaction medium wherein thetwo polyesters can be combined and heated, preferably at temperaturesfrom 160° to 200° C., for a time sufficient to substantially completethe reaction. The time needed will depend upon the precise nature of thereactive materials. If desired, a reaction catalyst, such as dibutyltinoxide, can be added to improve the speed of the radical reaction.

The relative amounts of the polyesters used in the above reaction canvary considerably. The amount BHDP-containing polyester used can rangefrom about 20% to about 90% by weight of the total composition, and theamount of unsaturated polyester can range from about 80% to about 10% byweight of the composition. It is preferred that the amount of theBHDP-containing polyester range from 40% to 60% by weight of thecomposition, and that the amount of the unsaturated polyester range from60% to 40%.

The BHDP-containing polyester can be prepared by polymerization of BHDPin any suitable fashion which gives the compound of Formula I above. Aprocess for preparing BHDP has been reported previously by Schroder etal., J. Prakt. Chem., 315;958(1973). The R group in the BHDP-containingpolyester of Formula I above can comprise any non-interfering aliphaticor aromatic group, but one preferred R group comprises a branched orunbranched alkyl group having 1 to 10 carbon atoms. Examples of suchgroups include methylene, bismethylene, trimethylene, tetramethylene,etc. When this R group is tetramethylene, the resulting polyester in theabove reaction will comprise recurring units of BHDP-adipate. Anotherpreferred R group in this reaction comprises aromatic hydrocarbons of 6to 12 carbon atoms. Examples of such groups include ortho, meta, orpara-phenylene, methylphenylene, ethyl phenylene, etc. When the R groupis p-phenylene, the resulting polyester is comprised of repeating unitsof BHDP-terephthalate.

Any unsaturated polyester can be used to combine with the BHDP-polyesterand form the cross-linked product of the present invention. Anunsaturated polyester suitable for use in the present invention can beformed as the condensation product of an unsaturated dibasic acid and apolyol, or of a dibasic acid and an unsaturated polyol. Illustrative ofthe unsaturated polyesters usable in the present invention arepoly(2,2,4-trimethyl pentanediol maleate), poly(neopentyl glycol adipatemaleate), poly(ethylene glycol maleate), poly(1,2-propylene glycolmaleate), poly(1,3-propylene glycol maleate), and poly(1,4-butanediolmaleate).

The compositions of the present invention can be made into coatingshaving excellent hardness, flexibility and solvent resistance. Aheat-curable coating is prepared by dissolving a BHDP-polyester and anunsaturated polyester in an organic solvent. An example of a suitablesolvent is a 70 to 30 percent solution of toluene and ethylene glycolmonoethyl ether acetate. The percentage of solids in the coatings canrange from about 10% to about 40%, with a 30% solids percentagepreferred.

The relative amounts of the polyesters used to form the coatingcompositions can vary considerably, and ranges from about 30%BHDP-polyester/70% unsaturated polyester to about 90% BHDP-polyester/10%unsaturated polyester. Where BHDP-terephthalate and poly(neopentylglycol adipate-maleate) are the polyesters used, an approximately 65%BHDP-terephthalate composition is found to have superior coatingproperties.

Coatings prepared by dissolving the two polyesters in suitable organicsolvents are preferably spray applied onto an article, such as a solidmetal surface, and cured by heating for a sufficient length of time. Thecuring temperature should be above be above 135° C., and is preferablyin the range of 160°-200° C. For a 30% solids solution of the polyesterreaction product, curing may be carried out by heating at about170°-180° C. for approximately 20-30 minutes.

The coatings of the present invention are observed to have excellentpencil hardness, solvent resistance, and flexibility. These propertiesare the result of two types of curing Diels-Alder and radical. This hasbeen shown in test coatings prepared wherein one of these two curingroutes was suppressed. When a free radical inhibitor was employed, theradical cross-linking reaction was suppressed and there was a decreasein the solvent resistance and the hardness of the cured coating.Additionally, when curing occurs at a temperature below that necessaryfor the Diels-Alder reaction, 135° C., the coatings are very brittle andhave poor impact resistance and flexibility, even when free radicalinitiators are used.

The compositions of the present invention can be formed into strongadhesives, particularly useful in metal-to-metal bonding. The adhesivesare formed by combining a BHDP-polyester with an unsaturated polyesterat temperatures of less than 100° C. Metal-to-metal bonds can be formedby applying a small amount of this formulation (0.3-0.4 g/sq.in. ofmetal) and then curing at a temperature above 135° C. Preferably, curingis carried out by heating the composition at a temperature of about170°-180° C. for about 20-30 minutes. The adhesive mixtures can beapplied either as a solid at room temperature or as a melt at 100° C. to130° C. and then cured.

The proportions of each polyester used in the adhesive formulation canvary considerably, and range from about 20% BHDP-polyester/80%unsaturated polyester to about 90% BHDP-polyester/10% polyester.

The following examples are set forth as illustrative of the presentinvention and are presented to more clearly show the principles andpractice of the invention.

EXAMPLE 1 Preparation of Poly(BHDP-Terephthalate)

Into a 4-necked, 1-liter flask fitted with a mechanical thermometer, N₂ebulator, and steam jacketed column packed with Berl Saddles and toppedwith a Dean-Stark trap and condenser are charged dimethyl terephthalate(220 grams, 1.14 moles), BHDP (300 grams, 1.36 moles) and dibutyltinoxide (1.4 grams). The mixture is heated at 180°-190° C. for 5.5 hours.A conversion of 94 percent is effected based upon methanol distilledoverhead. The solid yellow glass (viscosity 40,000 cp at 220° F.) has anaverage molecular weight of 2,060, an acid member of 1.2, and a hydroxylnumber of 51.3.

EXAMPLE 2 Preparation of Poly(BHDP-Adipate)

Into the resin cook apparatus described in Example 1 are chargeddimethyl adipate (200 grams, 1.15 moles), BHDP (302 grams, 1.37 moles),and dibutyltin oxide (1.0 gram). The mixture is heated at 180° C. for 4hours. A conversion of 93 percent is obtained based upon the methanoltaken overhead. The tacky polyester has an average molecular weight of1.974, an acid number of 2.4, and a hydroxyl number of 50.0.

EXAMPLE 3 Preparation of Poly(Neopentyl Glycol Maleate Adipate)

The resin cook apparatus described in Example 1 is charged withneopentyl glycol (NPG) (299 grams, 2.88 moles), maleic anhydride (1965grams, 2.0 moles), acipic acid (73 grams, 0.5 mole), and dibutyltinoxide (1.14 grams). The mixture is heated at 180°-190° C. for 15.5hours. A conversion of 80 percent is obtained based on the water takenoverhead. The polyester has an average molecular weight of 1,398, anacid number of 15.3, and a hydroxyl number of 77.1.

EXAMPLES 4 TO 9 Coatings from BHDP-Polyester/Unsaturated PolyesterReaction Products

Examples 4 through 9 are formulated by dissolving a BHDP polyester andan unsaturated polyester in toluene/ethylene glycol monoethyl etheracetate (70/30). The percentages of each polyester in the reaction byweight is indicated in parenthesis in Table I. The formulations arespray applied as approximately 30 percent solids onto Bonderite1000-treated cold rolled steel panels and cured for 20 minutes at 350°F. in a forced air oven. The coatings are evaluated 24 hours aftercuring. The results are given in Table I.

                                      TABLE I                                     __________________________________________________________________________                        MEK**                                                        Coating System                                                                         Thick.                                                                            Pencil                                                                            Double                                                                             Impact Resist.                                                                        1/8 In. Conical                              Ex.                                                                              (Weight Percent)                                                                       mls.                                                                              Hard.                                                                             Rubs F/R (In.-Lb)                                                                          Mandrel Flex                                 __________________________________________________________________________    4  BHDP-    1.0 2H  250+ 160/60  Pass                                            Terephthalate/                                                                TMPD-***                                                                      Maleate (64/36)                                                            5  BHDP-    1.0 H   250+ 160/60  Pass                                            Terephthalate/                                                                BHDP-Adipate/                                                                 TMPD-Maleate                                                                  (52/26/22)                                                                 6  BHDP-    1.0 2H  250+ 160/160 Pass                                            Terephthalate/                                                                BHDP-Adipate/                                                                 TMPD-Maleate                                                                  (58/13/29)                                                                 7  BHDP-    0.6 4H+ 250+ 160/160 Pass                                            Terephthalate/                                                                NPG-Adipate-                                                                  Maleate* (79/21)                                                           8  BHDP-    1.0 2H  250+ 160/160 Pass                                            Terephthalate/                                                                NPG-Adipate-                                                                  Maleate* (65/35)                                                           9  BHDP-    1.4 2H  150  150/150 Pass                                            Terephthalate/                                                                NPG-Adipate-                                                                  Maleate* (48/52)                                                           __________________________________________________________________________     *Mole ratio maleate/adipate: 4/1.                                             **MEK is methyl ethyl ketone.                                                 ***TMPD is 2,2,4trimethyl-1,3-pentanediol.                               

EXAMPLES 10 TO 15 Adhesives from BHDP-Polyester/Unsaturated PolyesterReaction Product

Examples 10 through 15 are formulated by blending the BHDP polyesterwith an unsaturated polyester at temperatures less than 100° C.Metal-to-metal adhesive bonds for lap shear strengths are prepared byplacing 0.3-0.4 gram of the formulation between 1 square inch of two1-inch by 5-inch strips of sixteen gauge cold rolled stainless steel.The strips are held together with two pinch clamps (Thomas, No. 18). Theadhesives are cured in a forced air dry oven for 30 minutes at 350° F.Shear strengths are meaured according to ASTM D1002. The T-peel testsare carried out according to ASTM 1876 with the following modifications:9-inch by 1-inch coupons (twenty-six gauge stainless steel) are employedwith a 6-inch bond length. All samples are tested 48-72 hours aftercuring. The results of these tests are illustrated in Table II.

                  TABLE II                                                        ______________________________________                                                                     Lap                                                                           Shear,  T-Peel,                                  Ex.   Sample (Weight Percent)                                                                              psi     pli                                      ______________________________________                                        10    BHDP-terephthalate/TMPD-Maleate                                                                      2,500   6-8                                            (42/58)                                                                 11    BHDP Adipate/TMPD Maleate (64/36)                                                                    1,040   --                                       12    BHDP Adipate/TMPD Maleate (46/54)                                                                    1,300   --                                       13    TMP-BHDP Adipate-terephthalate*/                                                                     1,000   --                                             TMPD-maleate (77/23)                                                    14    TMP-BHDP Adipate-terephthalate*/                                                                     1,960   --                                             TMPD-maleate (61/39)                                                    15    NPG Adipate Maleate/BHDP-                                                                            2,200   8-9                                            terephthalate (35/65)                                                   ______________________________________                                         *TMP-BHDP adipateterephthalate prepared by reacting dimethyl terephthalat     (0.75 mole), dimethyl adipate (0.75 mole), trimethylolpropane (0.45 mole)     at 180° C. for 2 hours, and reacting this product with BHDP (0.94      mole) for an additional 1.25 hours.                                      

What is claimed is:
 1. A heat-curable composition comprising:(a) a filmor fiber forming bis(2-hydroxyethyl)-dicyclopentadiene-containingpolyester comprising recurring units of the formula: ##STR6## wherein Ris an aliphatic or aromatic group; and (b) an unsaturated polyester;said composition being curable at a temperature above 135° C. to providea cross-linked, three dimensional polyester.
 2. A heat-curableconposition as claimed in claim 1 wherein the amount ofbis(2-hydroxyethyl)dicyclopentadiene-containing polyester is from about20% to about 90% by weight of the composition and the amount ofunsaturated polyester is from about 80% to about 10% by weight of thecomposition.
 3. A cross-linked, three dimensional polyester obtained byheating the composition of claim 1 at a temperature about 135° C.
 4. Across-linked, three dimensional polyester, as claimed in claim 3obtained by heating the composition at a temperature in the range of160° to 200° C.
 5. A composition as claimed in claim 1 wherein Rcomprises a branched or unbranched alkyl group of 1 to 10 carbon atoms.6. A composition as claimed in claim 5 wherein R is tetramethylene.
 7. Acomposition as claimed in claim 1 wherein R comprises an aromatichydrocarbon.
 8. A composition as claimed in claim 7 wherein R comprisesp-phenylene.
 9. A composition as claimed in claim 1 wherein theunsaturated polyester comprises the condensation product of anunsaturated dibasic acid and a polyol.
 10. A composition as claimed inclaim 1 wherein the unsaturated polyester comprises the condensationproduct of a dibasic acid and an unsaturated polyol.
 11. A compositionas claimed in claim 1 wherein the unsaturated polyester comprisespoly(2,2,4-trimethyl pentanediol maleate).
 12. A composition as claimedin claim 1 wherein the unsaturated polyester comprises poly(neopentylglycol adipate maleate).
 13. A heat-curable composition as claimed inclaim 1 further comprising an organic solvent.
 14. A heat-curablecomposition as claimed in claim 13 wherein the weight percentage ofsolids in the organic solvent is in the range of 10 to 40 percent.
 15. Aheat-curable composition as claimed in claim 13 wherein the amount ofbis(2-hydroxyethyl)-dicyclopentadiene-containing polyester is from about30% to about 90% by weight of the composition and the amount ofunsaturated polyester is from about 70% to about 10% by weight of thecomposition.
 16. A polyester comprising recurring units of the formula:##STR7## wherein R is an aliphatic or aromatic grouped and R' is astraight or branched chain aliphatic group of 2 to 12 carbon atoms, anaromatic group of 6 to 12 carbon atoms or a group of the formula:##STR8## wherein each R" is, independently, a straight or branched chainaliphatic group of 2 to 12 carbon atoms and R"' is a straight orbranched chain aliphatic group of 0 to 12 carbon atoms.
 17. Thepolyester of claim 16 wherein R and R' are each, independently, selectedfrom the group consisting of methylene; bismethylene; trimethylene;tetramethylene; ortho-, meta-, or para-phenylene, methylphenylene, andethylphenylene.